Treatment of hydrocarbons



Nov. 8, 1949 C, s, KELLEY 2,487,142

TREATMENT 0F HYDRocARBoNs Filed Nov. l2, 1946 Patented Nov. 8, 1949.

TREATMENT F HYDROCARBONS Carl S. Kelley, `Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware Application November 12, 1946, Serial No. 709,318

The invention relates to the removal of hydrogen fluoride from hydrocarbon mixtures containing the same. In one aspect this invention relates to the removal of hydrogen fluoride from organic mixtures containing in addition hydrogen and/or low-boiling hydrocarbons, especially low-boiling saturated hydrocarbons, such as ethane, methane and propane. In another aspect this invention relates to an improved process for the reaction of an alkylatable hydrocarbon with; an alkylating agent in the presence of a hydrogen fluoride alkylation catalyst to produce parafn hydrocarbons of higher molecular weight.

Hydrogen iluoride in the form of a liquid, commonly used as highly concentrated or substantially anhydrous hydrouoric acid, has recently come into prominence as a very important catalyst for numerous organic reactions. For example, it is used alone or in a mixture with minor amounts of a boron halide, such as boron fluoride, as a catalyst in the conversion of hydrocarbons, such as alkylation, isomerization, disproportionation, and the like, and is also used as a refining agent and/or a selective solvent to remove materials, such as organic iluorine compounds, sulfur compounds, and other non-hydrocarbon organic impurities from liquid hydrocarbon materials, such as emuents of a hydrocarbon-alkylation step, natural gasoline, lubricating oil fractions, and the like. In these and other processes the hydrogen fluoride is a valuable material which must be conserved and recovered from by-products, etc.

Perhaps the most important industrial process at the present time which involves the use of hydrofluoric acid as a catalyst is the alkylation of low-boiling parafllnic hydrocarbons, particularly isobutane and/or isopentane', with alkylating reactants, particularly low-boiling olens, such as vpropylene, various butylenes, various amylenes,

and/ or di-isobutylene and tri-isobutylene to form normally liquid paraiiins which generally have high octane numbers and are quite valuable as constituents of aviation fuels. In such alkylatlon processes the reactants are intimately contacted in the liquid phase at a temperature between about 50 and about 150 F. and sufllcient pressureto maintain the reactant in the liquid phase with liquid concentrated hydroiluoric acid for reaction periods ranging from about 1 tc about 30 minutes. The molar ratio of paraffin to olefin in the feed is usually between about 3:1 and about :1. The reaction effluent is passed to a settling zone where a liquid hydrocarbonrich phase and a heavier liquid acid-rich phase are formed and separated. A large portion of the 8 Claims'. (Cl. 260-676) liquid hydrouoric acid phase in the settling zone is recycled to the reaction zone, although a portion thereof is generally withdrawn and subjected to purication for the removal of such impurities as water and acid soluble oils. The hydrocarbon-rich phase containing dissolved hydrogen fluoride is subjected to fractional ldistillation to remove hydrogen fluoride which is generally present to the extent of about'0.5 to about 3 per cent by volume. The overhead from this distillation which comprises substantially an azeotropc mixture of hydrogen fluoride and low-boiling hydrocarbons is condensed whereby a hydrocarbonrich phase and a liquid hydrouoric-rich phase are formed. The hydrocarbon-rich phase may be returned to the reactor or to the distillation zone as reflux, etc., while the hydrogen fluoride-rich phase is returned to the reactor or to the settling ZOIle.

In another method ofoperation of an alkylation process as described in my copending application, Serial No. 651,963, filed March 4, 1946, now U. S. Patent 2,448,601, issued September 7, 1948, the hydrocarbon-rich phase containing dissolved hydrogen iiuoride is passed from the settling zone directly to a deisobutanizer. In this method of operation the step for the removal of hydrogen fluoride from the hydrocarbon-rich phase by distillation is omitted. In the deisobutanizer, isobutane and lighter hydrocarbons including hydrogen fluoride are recovered as an overhead product and normal butane and heavier hydrocarbons including some alkyl fluorides are removed as a bottom product. The bottom product is further treated to recover the alkylation product. The overhead product is passed to a depropanizer in which propane and lighter hydrocarbons are separated from isobutane. However, since hydrogen uoride is present in the feed stream to the depropanizer, an ole'nic hydrocarbon stream is introduced into the depropanizer in order that the olefin may react with the hydrogen fluoride to remove it with the bottom product. The resulting alkyl fluoride formed by the reaction of the oleiln with hydrogen iiuoride in the depropanzier is removed as a bottom product with the isobutane; thus, substantially all of the hydrogen fluoride is prevented from passing overhead with the propane. Contamination of the propane with hydrogen fluoride prevents use for many purposes such as a fuel, and also constitutes a loss of hydrogen fluoride. The isobutane and alkyl fluoride from the depropanizer may be returned to the reaction zone.

In the first method of operation in which hydrogen uoride is removed from the hydrocarbon stream by distillation, a portion of this overhead from the hydrogen uoride distillation zone is vented in order to prevent a build up of too high a pressure in the allwlationsystem. Such a build up of pressure is caused by-the accumulation" of light gases, such as hydrogen, methane, ethane and some propane. The venting of these gases carries with it hydrogen uoride, which factor constitutes an economical loss of hydrogen fluoride as well as a health hazard. Likewise hydrogen fluoride is lost with the propane overhead from the depropanizer in the second described operation even though the major portion of the hydrogen uoride is removed by reaction with the olein in the depropanizer. It is, therefore, desirable to remove the hydrogen iuoride from these streams, such as by caustic washing, in order to enable their future use. A

Hydrogen sulde and low-boiling mercaptans are also commonly found as contaminates or impurities in the overhead from the depropanizer in the second of the abovev discussed operations. In such case the hydrogen sulfide and mercaptans are introduced into the system with the olelnic hydrocarbon stream which often contains substantial proportions of these materials. Small amounts of hydrogen sulde and mercaptans may also contaminate the vent gases along with hydrogen uoride in the rst of the above described operations, although not to the extent found in the deprofpanizer overhead of the second operation, hydrogen sulfide and mercaptans being in the feed charged to the alkylation process but because of their conversion are primarily removed either with the liquid acid phase or liquid hydrocarbon phase as soluble materials. In removing hydrogen fluoride by a caustic wash solution of sodium hydroxide, the hydrogen sulde and mercaptans will also be removed which fact results in an increased and unnecessary consumption of Y the caustic wash solution. It is much to be desired to provide a method for removing hydrogen uoride without also removing hydrogen sulfide and mercaptans from a low-boiling hydrocarbcn stream containing same, both to decrease caustic consumption as stated and retain the benefits of the heating value which may be derived from the combustion of the sulfur compounds when the hydrocarbon stream is used as a fuel.

This invention is a continuation-in-part of my copending application Serial No. 651,963, led March 4, 1946, now U. S. Patent 2,448,601, issued September 7, 1948, in which a novel process for the alkylation of an isoparaiiin is described.

It is an object of this invention to improve the operation of a process for reacting a low-boiling isoparain with an alkylating agent.

4Another object of this invention is to remove propane from an alkylation process wherein hydrogen fluoride is employed as a catalyst without removing hydrogen uoride from the system at the same time. y

It is still a further object of this invention to remove hydrogen iiuoride from a low-boiling hydrocarbon stream containing hydrogen fluoride and hydrogen sulde without simultaneously removing the hydrogen sulde.

Another object of this invention is to provide a selective absorption process.

It ls still a further object of this invention to remove vaporous hydrogen iuoride from a gaseous mixture containing the same. 4 l

Yet another object of this invention is to remove hydrogen iiuoride from a liquid propane stream.

Y scription and disclosure.

According to my invention, I have found that hydrogen fluoride may be. selectively removed from a hydrocarbon mixture containing less than about one per cent hydrogen iiuoride and hydrogen sulde by contacting such -a Ymixture withY l a solution of sodium bisulflde, preferably a 2 to 4 per cent aqueous solution of` sodium bisulilde. The hydrocarbon mixture is contacted in an absorption zone, either in the liquid or vapor phase, by a liquid solution of sodium bisulde whereby hydrogenv fluoride combines with the sodium bisulde to form sodium fluoride and hydrogen sulfide. The sodium uorlde is removed with the liquid aqueous solution from the absorption zone and the hydrogen sulde formed in the absorption zone is removed with the hydrocarbon -mixture, which is substantially free'from hydrogen fiuoride.

My invention will now be further described and discussed in connection with the accompanying drawing which forms a part of this lapplication and which shows dlagrammatically, by means of a fiow sheet, an arrangement of apparatus suitable for use in practicing a preferred embodimen of my invention.

Referring now to the drawing, a parainic hydrocarbon stream having a high content of isoparaln to be alkylated is introduced through line I0 and a stream comprising oleflns to be reacted therewith is introduced through line I I. In practice, material entering through line I0 will comprise 90 to 98 per cent of a low-boiling isoparaiiln, such as isobutane and/or isopentane. The stream added through line II can be a butane-butene mixture, such as is often available in a refinery from elliuents of a cracking operation. In some instances it may also contain amylenes and/or some propylene,l although, as is evident from the present disclosure, when itis desired to react propylene, this will be added to the system at a different point, as will be more fully discussed hereinafter. When oleflnic polymers are available for reaction with a low-boiling isoparan, they may also be included in the feed passing through line I I or in some instances may constitute the/ sole or main part of the oleiins. Since most of these streams will contain some dissolved water they are combined and passed through dehydrator I2, which contains a suitable dehydrating agent such as alumina, bauxite, silica gel, calcium chloride, or the like. The dehydrated effluents pass through line I3, together with recycle isoparafn returned through line 34, to alkylator I4 wherein they are intimately admixed with a hydrofluoric acid catalyst. This catalyst is in` troduced to alkylator I4 through line I5 and in commercial operations will comprise a major por-` tion of recycled catalyst, which is returned to the process through line I6, and fresh hydrouoric acid introduced through line I1. The reactants are treated under alkylation conditions well known to the art, such as reaction time of about 5 to about 20 minutes, a. ratio of hydrocarbons to hydrouoric acid between about 2:1 and 1:2, a. reaction temperature between about and about F., and a. pressure sulcient to maintain the reactants substantially entirely in liquid phase.

The physical mixture of hydrofluoric acid. catalyst and hydrocarbons, containing unreacted parain hydrocarbons and products of the alkylation reactions. is passed from alkylator I4 through I6 and a major portion oi' it is recycled as previously discussed. Since this material tends to have accumulated in it, small amounts of water and various organic impurities of high molecular weight, a portion is generally discharged, either continuously or from time to time, through line 22 for such treatment as mayv be desired. A hydrocarbon phase, generally substantially entirely liquid, is withdrawn from the upper portion of settler 2| through line 23 and passed to a deisobutanizer feed tank 24. This feed tank acts primarily as a surge tank, or accumulator, so that a steady flow of material to deisobutanizer 21 can be eifected even though variations may be experienced in the operations of the equipment just discussed. In some instances a small amount of hydrouoric acid may settle out in the bottom of this feed tank in which case it can be returned to the alkylation system by being passed through line 25 to line I6.

The hydrocarbon mixture, containing substantially only dissolved hydrofluoric` acid, is passed from feed tank 24 through line 26 to deisobutanizer 21. This can be any suitable type of conventional fractional distillation column so designed that it will resist the corrosive action of hydroiiuoric acid and will produce as .an overhead product substantially all of the isobutane and lower-boiling hydrocarbons together with free hydrogen fluoride contained in the charge entering through line 26. Although hydrogen fluoride has a higher boiling point than isobutane, it forms a minimum-boiling azeotropic mixture with lowboiling paraffin hydrocarbons, as disclosed in Frey 2,322,800, issued June 29, 1943, and the small to an und ble high concentration and reduce of the plant, and may necesssita'te` an increase in the operation pressure. A portionthe eiiici of the isobutane fraction, therefore. is withdrawn from line 33, through line and passed to depropanizer 3l.

ride and to effect la separation betweenpropane and lighter hydrocarbons and isobutane. Howe v ever, since someoi the hydrogen fluoride will a tend to be contained in the overhead product.

an olefin-containing materlalis added to depropanizer 36 through line 40. In accordance with a preferred embodiment of this invention,

this olefin-containing material is a propanepropylene mixture. When this fraction issub- -stantially free from Cz and lighter hydrocarbons, it may be added at an intermediate part of de.- propanizer 36, such as by being added through line 4I directly to the feed line 35. However. in order to prevent contact between any ethylene which may be present and any large proportion ofthe hydrogen fluoride entering depropanizer through line 35, it is preferred to add this ma.

. the excess is discharged from the system through amount which is present inthe feed to the deisobutanizer will readily pass overhead along;

in condenser 3 I, and passed to reflux accumulator 32. A substantial portion is withdrawn through line 33 and returned to the top of deisobutanizer 2l as liquid reflux. Since the hydrocarbon material passing through line 26 is a saturated solution of hydrogen fluoride in hydrocarbons, and since a substantial portion of this hydrocarbon material is too high boiling to be present in the overhead fraction, there may be present more than sufficient hydrogen fluoride to form a saturated solution, and as a result, some separated liquid hydrogen fluoride will settle out in the bottom of reflux accumulator 32. This material, together with a substantial portion of the isobutane, is removed from the bottom of accumulator 32 through line 34 and returned to line I3 and alkylator I4 for' reintroduction into the reaction zone. This stream will comprise the desired recycle isobutane stream.

In commercial operations it is substantially inevitable that some propane and lighter material will be present in one or more of the streams added through line I0 and/or Il. Unless some provision is made for removing this material from the system, it will tend to accumulate line 41. In many instances the material added through line 40 will contain more propylene than is molecularly equivalent-to the hydrogen fluoride concomitantly entering the depropanizer through line 35, to ensure that the overhead product is essentially free from free hydrogen fluoride.

j' f The' propane stream in accumulator 45 will conl tain'a small amount of hydrogen iluoride together with `'hydrogen sulfide and low-boiling mercaptans'fderived from the olefin-containing material-introduced into depropanizer 36 through line 4i).` Since it is desirable to selectively remove the hydrogen fluoride, the propane stream is passedpyto'jcaustic washer 52, as a liquid through line 4ly or as a vapor through line 49, whichever is desired. In caustic washer 52, the hydrocarbon stream, in either the liquid or the vapor phase, is contacted countercurrently with a down flowing aqueous solution of sodium bisulde entering through line 53. In liquid phase operation relatively high super-atmospheric pressures and relatively low temperatures are used and vapor phase operation is conveniently effected under similar conditions of temperature and pressure. By intimate contact between the sodium bisulflde solution and the propane stream, the hydrogen fluoride is selectively removed from the propane and hydrogen sulfide. Caustic solution containing sodium fluoride is removed from caustic Washer 52 through line 56 while the treated propane stream substantially free from sodium fluoride but containing hydrogen sulfide and low-boiling mercaptans is removed through line 54. 'I'he purified propane stream may be used as a reactant or as a fuel.

'I/he kettle product of depropanizer 36 comprises primarily isobutane and propyl fluoride.

Depropanizer 36 is anyv desired type of fractional distillation column designed'to g withstand the corrosive action of hydrogen uo-..

aiszne In some instances, particularly hns, particularly butylenes, to a'. low portion-0L 10 depropanizer 36, as through line 46.

The kettle product from deisobutanizer 21 comprises the higher-boiling paraflin hydrocarbons produced in alkylator I4 and most of the normal butane which may be present in the eiliuents of the reaction zone. This material is passed from the kettle of deisobutanizer 21 through line 6I to deiiuorinator 62, wherein it is treated to remove any iiuorine compounds which may be contained therein. This may be satisfactorily effected by contacting the stream with a material such as alumina, or bauxite, as disclosed in Frey 2,347,945, issued May 2, 1944, at about the same temperature as is used in the kettle of deisobutanizer 2'1. In the event that bauxite is used and the conditions are such that there is danger of silicon tetraluoride being present in the eiiluents of deluorinator 62, lime may be included as a part of the contact mass. A substantially vfiuorine-free eiiuent is passed through line 63 to suitable separating means illustrated by fractionator 64. Normally butane is discharged from the system through line 65, a light alkylate friction is recovered through line 66 as a product of the process, anda heavy alkylate fraction is recovered through line 61, also as a product of the process. These materials may be subjected to any desired subsequent treatment and may be blended with other motor fuel ingredients to produce a premium motor fuel as is well known in the art.

The sodium bisulde solution used to selectively absorb the hydrogen fluoride from the hydrocarbon stream containing the same together with hydrogen sulde and low boiling mercaptans may be made by mixing a 3 per cent solution of sodium hydroxide with hydrogen sulfide. The concentration of the sodium bisulde may be determined at any time in the caustic Washer by titrating the wash solution with standard hydrochloric acid using an indicator which changes color at a pH of less than 6.

It will be appreciated that this drawing is diagrammatic and there may be conventional pieces of equipment, such as heating chambers, lreboilers, extra reaction zones, extra dehydrating equipment, deuorinating equipment, fractional -distillation zones, coolers, and the like which have not been shown. However, such equipment may be supplied by those skilled in the art without departing from the scope of this invention and the drawing furnishes a sufiicient guide to one skilled to practice the invention successfully.

tion.

The following example illustrates a specific embodiment of this invention. It is understood, however, that such example should not be interpreted as having an unnecessary limitation to the invention.

Example I msumde. Table 1 below snows a typical com'- position of such a low-boiling hydrocarbon fraction:

Component: Liquid volume, cent Ethylene 1 Ethane 10 Propylene 9 Propane 79 Butane v 1 Total Weight, per cent H28 0.2

When the above hydrocarbon lstream was washed with a caustic solution of sodium hydroxide at approximately atmospheric conditions of temperature and pressure in the conventional manner, the sodium hydroxide consumption is 434 pounds per 1,000 barrels of hydrocarbon and both the hydrogen sulfide and the hydroiiuoric acid are removed. When the hydrocarbon mixture is washed with sodium bisultldc as herein before described, 47 pounds per 1,000 barrels of hydrocarbon is consumed and this may be made from about 34 pounds of sodium hydroxide. None of the hydrogen sulfide was removed; whle the hydrogen iuoride was removed, the hydrogen uoride remaining in the hydrocarbon stream being less than 0.0005 weight per cent. The sodium bisulfide wash solution is discarded when the pH drops below about 7.2 and replaced by a 3 per cent sodium bisuliide solu- I claim:

1. The process for selectively removing h drogen fluoride from an organic mixture comprising propane and lighter hydrocarbons, hydrogen sulfide and hydrogen fluoride which comprises contacting said organic mixture in the liquid phase with approximately a. 2 to 4 per cent solution of sodium bisulde in water underconditions such that the hydrogen fluoride inv said organic mixture is selectively absorbed by said solution of sodium bisulfide and recoveringan organic mixture substantially free from hydrogen uoride but containing hydrogen sulde.

2. The process for 'selectively removing hydrogen uoride from an organic mixture comprising propane and lighter hydrocarbons, hydrogen sulfide and hydrogen iiuoride which comprises contacting said. organic mixture with solution of sodium bisulde in water under conditions such that the hydrogen fluoride in said organic mixture is selectively absorbed by said solution of sodium' bisulfide and recovering an organic mixture substantially free from hydrogen iiuoride but containing hydrogen sulfide.

3. The process for selectively removing hydrogen fluoride from an organic mixture containing hydrogen sulflde and hydrogen fluoride and which is immiscible with water and inert with respect to sodium bisuliide which comprises contacting said organic mixture in the liquid phase with approximately a 2 to 4 per cent solution of sodium bisulide in water under conditions such that the hydrogen uoride in said organic mixture is selectively absorbed by said solution of sodium bisulde and recovering an organic mixture substantially free from hydrogen uoride but containing hydrogen sulde.

4. The process for selectively removing hydrogen fluoride -from an organic mixture contain.

from an organic mixture containing the same,

and which is immiscible with water and inert with respect to sodium bisulde which comprises contacting said organic mixture with solution of sodium bisulde in water under conditions such that the hydrogen nuoride in said organic mix- 10 ture is absorbed by said solution of sodium bisulde and recovering an organic mixture substantially free from hydrogen fluoride.

6. A process of preparing a hydrogen fluoridefree light hydrocarbon stream comprising propane whichcomprisesv contacting such stream i'rom the effluent of an alkylation reaction between isobutane and a low-boiling olefin in the presence of a hydrogen fluoride alkylation cata.- lyst with a solution of sodium bisulde in Water under conditions such that the hydrogen fluoride in said hydrocarbon stream is absorbed by said sodium bisulde and recovering said light hydrocarbon stream free roi hydrogen fluoride. y

. CARL S. KELLEY. 

